US4098691A - Purification of water for boiler - Google Patents

Purification of water for boiler Download PDF

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Publication number
US4098691A
US4098691A US05767438 US76743877A US4098691A US 4098691 A US4098691 A US 4098691A US 05767438 US05767438 US 05767438 US 76743877 A US76743877 A US 76743877A US 4098691 A US4098691 A US 4098691A
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Prior art keywords
water
resin
organic
molecules
ozone
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US05767438
Inventor
John Filby
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Canada Minister of Energy Mines and Resources
Ontario Energy Corp
Gulf Canada Ltd
Canada Cities Service Ltd
Imperial Oil Ltd
Original Assignee
Ontario Energy Corp
Canada Cities Service Ltd
Gulf Oil Canada Ltd
Imperial Oil Ltd
Canada Minister of Energy Mines and Resources
Canada Cities Service Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/78Treatment of water, waste water, or sewage by oxidation with ozone
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04Processes using organic exchangers
    • B01J41/05Processes using organic exchangers in the strongly basic form

Abstract

Ozone is dispersed in river water to be purified and used in a high pressure boiler. The ozone selectively degrades large organic molecules, dissolved in the water, which ordinarily will irreversibly foul the strongly basic anion attracting resin used to adsorb silicious contaminants from the water. The degraded molecules are reduced in resin-fouling capability and are removed from the resin during regeneration.

Description

BACKGROUND OF THE INVENTION

This invention relates to a process for purifying raw water, containing dissolved organic molecules of high molecular weight and silicious contaminants, to render it suitable for use as boiler feed.

In purifying raw water, such as river or lake water, special consideration must be given to the removal of silica in its various forms. Usually the silica is dissolved to some extent and is present in the water as silicic acids. When the untreated raw water is introduced into a boiler, the silicic acids tend to be converted to silica, which forms a solid deposit on the boiler surfaces. This deposit detrimentally interferes with heat transfer within the boiler.

In modern high pressure boilers, which operate at elevated water temperatures, silica and its related compounds (collectively termed ` silicious contaminants`) pose a further problem. Several silicious contaminants are volatile at the temperatures at which high pressure boilers operate and can be carried in the evolving steam, to be deposited in solid form on equipment and pipes through which the steam passes.

It is a well-established feature of boiler operating art that silicious contaminants in boiler feed water may be conveniently removed by contacting the water with a strongly basic anion-attracting exchange resin. The silicious contaminants are adsorbed by the resin.

Before the raw water is contacted with resin, such water is usually treated to remove most of the minerals ("softening") and insoluble organic materials ("clarifying"). This pre-treatment is done by contacting the raw water with certain chemicals, commonly one or more of: lime, alum, carbon, sodium aluminate, and clay. The treatment is done before the water contacts the resin, as the minerals and organic substances themselves tend to be adsorbed onto the resin with the consequence that the resin will rapidly foul and will need regeneration. Regeneration usually involves contacting the resin with a base, such as sodium hydroxide.

A further step in the pre-treatment is contacting the raw water with chlorine to kill obnoxious bacteria.

The combination of traditional pre-treatment and contact with resin has been effective in purifying most types of water used as boiler feed. However, a problem arises when the raw water, besides containing silicious contaminants, also contains significant quantities of large dissolved organic molecules, which is the case when the water originates from regions where drainage areas are swampy. These organic molecules are thought to be humic acid or analogues thereof. In any event, the organic molecules are substantially unaffected by the conventional pre-treatment process; instead, they are adsorbed by the resin and foul it. When the resin is regenerated, these organic molecules are only partly removed by the first regeneration and less completely with subsequent regenerations, with the resin rapidly being rendered useless.

A probable reason for the organic molecules' affinity for the resin is that such resins are manufactured with a high pore volume at the surface to encourage ion exchange; it is believed that this porous structure offers sites where the large organic molecules can adhere to the resin.

Two known methods have been heretofore available for removing the offending water-soluble organic molecules. The first method involves contacting the raw water with adsorbant activated charcoal. However, this method is impractical for large flows. The second method involves contacting the raw water with a weakly-basic anion attracting resin. This resin extracts substantially all organic molecules from the water, after which silicious contaminants may be removed in the usual way with a strongly basic resin. The guard resin may be periodically regenerated, but its use is characterized by: high capital cost, frequent regeneration, and frequent testing to monitor the effectiveness of the guard resin.

SUMMARY OF THE INVENTION

In accordance with the present invention, raw water containing silicious contaminants and high molecular weight water-soluble organic molecules, the latter usually having a molecular weight of 6,000 or greater, is contacted with ozone, before the water is contacted with the strongly-basic anion attracting resin. The ozone is dispersed in the water in sufficient quantity as to degrade larger organic molecules, with the result that the resin may satisfactorily be regenerated in conventional manner, as by contacting it with sodium hydroxide. Preferably the ozone is provided in an amount less than 2 parts per million by weight/per part per million by weight carbon present in the water as total organic carbon.

The invention is characterized by several advantages. Firstly, it appears that the ozone is selective in degrading the large organic molecules without significantly attacking the degradation products -- thus the invention can be practised without a high consumption of ozone. Secondly, the ozonized organic molecules are significantly less intense in their resin-fouling properties, thereby making it possible to use the resins longer before regeneration is needed. Thirdly, because ozone is a powerful oxidizing agent, the need for chlorine pre-treatment is reduced or eliminated, thereby simplifying the water treatment operations. Finally, the process is relatively simple and inexpensive and does not require careful monitoring.

DESCRIPTION OF THE DRAWINGS

In the drawings FIG. 1 is a block diagram illustrating the sequence of steps for a preferred form of the invention; and

FIG. 2 is a diagrammatic illustration of the invention as practised on the pilot run.

DESCRIPTION OF THE PREFERRED EMBODIMENT

The pilot circuit A shown in FIG. 2 had been fed raw water taken from the Athabasca River in Alberta. The drainage area for this river is characterized by large areas of swamp (known locally as "muskeg") and the water was contaminated with appreciable quantities of mildy acidic organic material -- it contained 10 -- 30 ppm as total organic carbon (TOC). It was found that, without ozonation, the strongly basic resin would foul and become inoperative with 12 hours of operation. The resin was considered exhausted when a sudden rise was noted of the conductivity of the emerging water in conjuction with a drop in pH. The resin was regenerated once and operated satisfactorily, however within 12 hours it was exhausted and, when contacted with regenerating base, was ineffective for ion exchange.

The invention was then practised as follows. A laboratory plate-type ozonator 1 (Grace* model, LG-2-L1, capacity 100 grams ozone per day) was used to disperse ozone into a contact column 2 having a diameter of 7 cm. and height of 200 cm. The ozone produced by the ozonator 1 was introduced into column 2 through a porous glass diffuser 3 placed at the raw water intake 4. Excess ozone was removed from the column 2 through an overhead line 5 and decomposed in a tube furnance 6 packed with quartz chips and maintained at 1000° C. The ozonated water was then passed through the conventional water treatment circuit A comprising a weak acid cation-attracting resin column 7, a strong acid cation-attracting resin column 8 and the strong base anion-attracting resin column 9. Athabasca River water, which had been held in a storage tank, was fed to the column 2 at the same rate as had been the case before the ozonator circuit B had been installed, i.e. 200 cm3 /minute. This water contained 30 ppm TOC. The test was carried out for a period of 6 days, with the strongly-basic resin being regenerated daily without noticeable decrease in its efficiency.

A particular advantage of the invention is that only enough ozone has to be added to the feed water to degrade the large molecules, without the need for organic molecules to be oxidized all the way to carbon dioxide. This was demonstrated by analysis. On treating raw water with from 5 to 6 ppm ozone the total organic carbon (TOC) was reduced from fifteen ppm to fourteen ppm. Analysis of duplicate samples by the ultraviolet technique (UV) at 225nm, however, showed that UV absorption in the ozone treated water was only about half the level of the untreated water. Since small molecules absorb less than larger molecules the diminished UV absorbance after ozone treatment is an indication of degration of the humic and fulvic acids. On the other hand the only slight diminution in TOC reveals that very little of the organic material was vapourized to carbon dioxide. The selectivity whereby ozone preferentially degrades the larger organic molecules ensures that the invention is highly efficient in the use of ozone.

Claims (4)

What is claimed is:
1. In the process in which raw water, containing silicious contaminants and dissolved organic molecules having a molecular weight in excess of 6000, is treated with strongly basic anion-attracting exchange resin to remove substantially all said silicious contaminants to prepare said water for use as boiler feed, said resin being subjected to periodic regeneration when its ion exchange capacity is reduced by use, the improvement which comprises:
dispersing ozone in said raw water, before the water is contacted with the strongly basic resin, said ozone being added in sufficient quantity as to degrade the organic molecules to species of lower molecular weight whereby the resulting degraded organic molecules after adsorption on said strongly basic resin may be removed by regeneration with a strong base.
2. Process according to claim 1 comprising:
contacting, used, ineffective resin, previously contacted by ozonated water, with a regenerating solution of strongly basic, water soluble substance, thereby converting said resin to an effective reusable condition.
3. Process according to claim 2 comprising:
contacting the resin with purified water to wash out residual amounts of said strongly basic water soluble substance to prepare said resin for further use in removal of silicious contaminants from raw water.
4. Process according to claim 1 wherein:
the quantity of ozone used is not more than 2 parts per million by weight for every part per million by weight of carbon present in said raw water as total organic carbon.
US05767438 1977-02-10 1977-02-10 Purification of water for boiler Expired - Lifetime US4098691A (en)

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4172786A (en) * 1978-09-29 1979-10-30 Nasa Ozonation of cooling tower waters
US4296075A (en) * 1978-11-24 1981-10-20 Mobil Oil Corporation Method for protecting an ion-exchange resin from chemical poisoning
US4298578A (en) * 1978-11-24 1981-11-03 Mobil Oil Corporation Leach method including means to protect ion exchange resin
US4495152A (en) * 1978-11-24 1985-01-22 Mobil Oil Corporation Leach apparatus including means to protect ion exchange resin
WO1985002605A1 (en) * 1983-12-16 1985-06-20 Ecolochem, Inc. Deoxygenation process and apparatus
US4602999A (en) * 1983-11-08 1986-07-29 Chemirite Method for removing a silicic compound from the waste liquor of steel pickling
US4696739A (en) * 1984-04-02 1987-09-29 Aqua Strip Corporation Water purification apparatus
EP0284944A1 (en) * 1987-04-02 1988-10-05 Siemens Aktiengesellschaft Process for changing the capacity of an ion exchanger for a particular chemical element
US4818411A (en) * 1983-12-16 1989-04-04 Ecolochem, Inc. Deoxygenation process
US4969520A (en) * 1989-06-26 1990-11-13 Mobil Oil Corporation Steam injection process for recovering heavy oil
US5106497A (en) * 1990-11-07 1992-04-21 Advanced Oxidation Systems, Inc. Ozone treatment system utilizing an air lift pump as a mixer and as a circulating means
US5186841A (en) * 1991-11-05 1993-02-16 Praxair Technology Inc. Cooling water ozonation system
US5271837A (en) * 1992-04-22 1993-12-21 Discepolo Carl G Drinking water filtration system
EP0670184A2 (en) * 1994-03-01 1995-09-06 Mitsubishi Chemical Corporation Method of demineralizing water or an aqueous solution
US5505856A (en) * 1989-05-23 1996-04-09 Eco Purification Systems, Bv Process for the purification of contaminated water by activated ozone
US5665228A (en) * 1996-01-22 1997-09-09 Dimension One Spas, Inc. Ozone mixing system for a hydrotherapy spa
US5753494A (en) * 1995-09-29 1998-05-19 Waste Management, Inc. Method and apparatus for treating contaminated soils with ozone
US5785864A (en) * 1995-06-23 1998-07-28 Ajt & Associates, Inc. Apparatus for the purification of water and method therefor
US6090294A (en) * 1995-06-23 2000-07-18 Ajt & Associates, Inc. Apparatus for the purification of water and method therefor

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US897039A (en) * 1907-04-23 1908-08-25 Alfred Vogelsang Process for purifying and filtering water.
US1341913A (en) * 1918-12-23 1920-06-01 Ozone Company Of America Process for removing phenol and other aromatic hydrocarbons from water or other liquids
US2669713A (en) * 1950-10-27 1954-02-16 Dow Chemical Co Method of regenerating anion exchange resins
US3635817A (en) * 1968-10-17 1972-01-18 Envirotech Corp Waste water treatment process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US897039A (en) * 1907-04-23 1908-08-25 Alfred Vogelsang Process for purifying and filtering water.
US1341913A (en) * 1918-12-23 1920-06-01 Ozone Company Of America Process for removing phenol and other aromatic hydrocarbons from water or other liquids
US2669713A (en) * 1950-10-27 1954-02-16 Dow Chemical Co Method of regenerating anion exchange resins
US3635817A (en) * 1968-10-17 1972-01-18 Envirotech Corp Waste water treatment process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Kunin, R., Ion Exchange Resins, N.Y., R. E. Krieger, 1972, pp. 382-383. *

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4172786A (en) * 1978-09-29 1979-10-30 Nasa Ozonation of cooling tower waters
US4296075A (en) * 1978-11-24 1981-10-20 Mobil Oil Corporation Method for protecting an ion-exchange resin from chemical poisoning
US4298578A (en) * 1978-11-24 1981-11-03 Mobil Oil Corporation Leach method including means to protect ion exchange resin
US4495152A (en) * 1978-11-24 1985-01-22 Mobil Oil Corporation Leach apparatus including means to protect ion exchange resin
US4602999A (en) * 1983-11-08 1986-07-29 Chemirite Method for removing a silicic compound from the waste liquor of steel pickling
US4556492A (en) * 1983-12-16 1985-12-03 Ecolochem, Inc. Deoxygenation process
US4818411A (en) * 1983-12-16 1989-04-04 Ecolochem, Inc. Deoxygenation process
WO1985002605A1 (en) * 1983-12-16 1985-06-20 Ecolochem, Inc. Deoxygenation process and apparatus
US4696739A (en) * 1984-04-02 1987-09-29 Aqua Strip Corporation Water purification apparatus
EP0284944A1 (en) * 1987-04-02 1988-10-05 Siemens Aktiengesellschaft Process for changing the capacity of an ion exchanger for a particular chemical element
US5505856A (en) * 1989-05-23 1996-04-09 Eco Purification Systems, Bv Process for the purification of contaminated water by activated ozone
US4969520A (en) * 1989-06-26 1990-11-13 Mobil Oil Corporation Steam injection process for recovering heavy oil
US5106497A (en) * 1990-11-07 1992-04-21 Advanced Oxidation Systems, Inc. Ozone treatment system utilizing an air lift pump as a mixer and as a circulating means
US5186841A (en) * 1991-11-05 1993-02-16 Praxair Technology Inc. Cooling water ozonation system
US5271837A (en) * 1992-04-22 1993-12-21 Discepolo Carl G Drinking water filtration system
EP0670184A2 (en) * 1994-03-01 1995-09-06 Mitsubishi Chemical Corporation Method of demineralizing water or an aqueous solution
EP0670184A3 (en) * 1994-03-01 1995-09-27 Mitsubishi Chem Corp
US5785864A (en) * 1995-06-23 1998-07-28 Ajt & Associates, Inc. Apparatus for the purification of water and method therefor
US6090294A (en) * 1995-06-23 2000-07-18 Ajt & Associates, Inc. Apparatus for the purification of water and method therefor
US5753494A (en) * 1995-09-29 1998-05-19 Waste Management, Inc. Method and apparatus for treating contaminated soils with ozone
US5665228A (en) * 1996-01-22 1997-09-09 Dimension One Spas, Inc. Ozone mixing system for a hydrotherapy spa

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Owner name: GULF CANADA LIMITED

Free format text: CHANGE OF NAME;ASSIGNOR:GULF OIL CANADA LIMITED;REEL/FRAME:003962/0723

Effective date: 19780508